Material for protective film formation and method of forming resist pattern therewith

Abstract

A material for protective film formation that is used to form an upper-layer protective film for a resist film and that contains at least a polymer component soluble in water or alkali and an alcohol containing a fluorine atom; and a method of forming a resist pattern with the use of the same. Consequently, not only can the degeneration of resist film during liquid immersion exposure by various liquids for liquid immersion exposure, for example, water and the degeneration of liquid immersion exposure liquids per se be simultaneously prevented in the liquid immersion exposure process, but also without inviting an increase of the number of processing steps, the resistance to post exposure delay of the resist film can be enhanced.

1 . A material for forming a protective film of a resist film top layer comprising: a water-soluble or alkali-soluble polymer component; and a fluorine atom containing alcohol. 
   
   
       2 . The material according to  claim 1 , wherein the resist film is subjected to a liquid immersion lithography process. 
   
   
       3 . The material according to  claim 1 , wherein the fluorine atom containing alcohol has the number of the fluorine atoms larger than that of the hydrogen atoms included in the molecule thereof. 
   
   
       4 . The material according to  claim 1 , wherein the fluorine atom containing alcohol has 4 to 12 carbon atoms. 
   
   
       5 . The material according to  claim 1 , the fluorine atom containing alcohol is an alcohol represented by the following chemical formula (1):
   C 4 F 9 CH 2 CH 2 OH  (1), and/or   an alcohol represented by the following chemical formula (2):
   C 3 F 7 CH 2 OH  (2). 
   
   
   
       6 . The material according to  claim 1  further comprising a crosslinking agent. 
   
   
       7 . The material according to  claim 1  further comprising an acidic component. 
   
   
       8 . The material according to  claim 7 , wherein the acidic component is a fluorocarbon compound. 
   
   
       9 . The material according to  claim 2 , wherein the resist film is exposed to a light in the liquid immersion lithography process through a liquid for liquid immersion lithography having a predetermined thickness and a refractive index higher than that of air and lower than that of the resist film, which is intervened in a pathway allowing the exposure light for lithography to reach the resist film. 
   
   
       10 . A method for forming a resist pattern using a liquid immersion lithography process comprising the steps of:
 forming a resist film on a substrate;   forming a protective film on the resist film using the material for forming a protective film according to  claim 1 ;   placing the liquid for liquid immersion lithography at least on the protective film of the substrate laminated with the resist film and the protective film;   selectively irradiating light to the resist film through the liquid for liquid immersion lithography and the protective film; performing a heat treatment if necessary; and   subjecting the protective film and the resist film to a developer treatment using an alkaline developer solution so as to simultaneously remove the protective film and obtain the resist pattern.